Spectroscopic study of the interaction of heavy metals with organic acids

The ongoing progress in spectroscopic methods of analysis has resulted in a growing interest in the nature of pollutants and hence the possibility of controlling their levels in the environment. This paper describes a study of the fate of some pollutants in both soil and water at two selected areas in the north of Cairo, Egypt. Samples were collected from Shoubra Elkhima and Kafr ElSheikh during October 2003 and October 2004, respectively. Atomic absorption spectrometry was used to evaluate the level of cadmium, chromium, copper, iron, lead and zinc in the collected samples. In addition, Fourier transform infrared spectroscopy was used to investigate the molecular structure of soil samples. Results indicate that there is a possible interaction between heavy metals and humic acid, which is manifested by a noticeable shift in the absorption of the carboxyl group towards lower frequencies as a result of metal interaction. Furthermore, it is concluded that the carboxylate group of humic acid leads the transport of metals from soil to groundwater.     

Studies on the effects of some organic pollutants on the heavy metal transport in an Indian soil

The translocation of some heavy metals, such as Hg, Cd, Cu, Co, Ni and Zn, as affected by organic pollutants, i.e. methanol, ethanol, propanol, formaldehyde, acetaldehyde, benzaldehyde, acetone, ethyl methyl ketone and cyclo-hexanone, was studied in an Indian red soil using soil thin layer chromatography. It was observed that an increase in the concentration of organic compounds in developer enhances the heavy metal mobility, except in the case of Cu and Hg which show a decreasing trend. The results are discussed in relation to the physico-chemical characteristics of the soil and adsorption/desorption phenomena.     

施用典型有机固废生物炭对土壤重金属生物有效性的影响

将有机固废经热解转化为生物炭,具有改良土壤、促进碳固定、钝化重金属等优点,但有机固废生物炭中被钝化重金属进入土壤后生物有效性尚不明确。采用盆栽方法评估了施用市政污泥、中药渣等典型有机固废生物炭对受纳土壤中重金属有效性及植物吸收、传输重金属的影响。结果表明,施用污泥炭、中药渣炭显著增加了土壤中As、Zn的化学提取有效态含量,从而降低了Cr、Pb有效态含量(P < 0.05),对Cd、Cu、Ni有效态含量也有不同程度的降低趋势;同时,抑制了除Zn以外As、Cd、Cr、Cu、Ni、Pb等6种重金属从土壤向植物的传输、累积,降幅最高达30%。中药渣炭联合污泥炭施用可进一步抑制7种重金属在植物地上部分以及除As、Cr外其他重金属在根中的吸收、累积。本研究结果可为评估有机固废生物炭土地利用的环境风险提供参考。     

灯心草部分生理生化指标对土壤复合重金属胁迫的响应

通过盆栽试验,以叶绿素含量和POD、SOD、CAT3种抗氧化酶活性作为观测指标,研究了Cu、Cd、Pb、Zn和As复合重金属胁迫下灯心草部分生理生化指标的变化趋势和机理.结果表明,灯心草的生理毒害效应呈明显的剂量-效应关系.表现为与对照相比,叶绿素含量减少,叶绿素a/b值降低,叶片失绿现象明显.随着复合重金属胁迫浓度的增加,灯心草3种酶活性均呈先升后降的变化趋势,但出现抗性酶活性高峰所对应的重金属浓度不同,表现出不同的特征变化趋势.总体来说,在接近土壤环境质量标准低浓度设计范围内,酶活性有逐渐被激活的趋势.但在高浓度水平下,酶活性普遍受到抑制.生长在铅锌尾矿和模拟矿毒水污染土壤中的灯心草叶绿素合成受到显著抑制(P＜0.05),但POD和CAT两种酶活性均高于对照.     

热解吸工艺放置顺序对土壤重金属稳定化效果的影响

为了研究热解吸工艺放置顺序对土壤重金属稳定化效果的影响,通过小试模拟的方式,对不同种类的土壤样品进行实验,对比分析了土壤的关键指标在加热前后的变化。结果表明,当热解吸工艺放置在添加稳定化药剂前时,会提高土壤的pH,也会使土壤的重金属有效态质量分数和酸浸出质量浓度增加,但仅有较低的可能性使2者超标。并且,根据不同的土壤酸碱性质,热解吸工艺对重金属形态转化产生的影响不同。当热解吸工艺放置在添加稳定化药剂后,不影响土壤重金属有效态含量和浸出浓度,并对重金属的形态转化没有影响。2种技术联用时的顺序对重金属稳定化效果的影响较小。本研究可为工程项目实施时的工艺设计提供参考。     

中国商品有机肥重金属分析

测定了来自10个地区不同生产原料的118个商品有机肥样品的重金属含量.结果表明:(1)商品有机肥样品中的Cd、Hg、Pb、Cr、As、Zn、Cu、Ni的平均值分别为0.600、0.120、7.34、84.30、9.45、202.91、91.06、11.01 mg/kg.(2)河南、湖北、上海的商品有机肥中8种重金属平均值均较高;内蒙古的商品有机肥中Cr平均值为20.32 mg/kg,广西的商品有机肥中Zn平均值为51.36mg/kg,远低于所有样品中Cr和Zn平均值.(3)以猪粪为主要生产原料的商品有机肥中重金属平均值最高.(4)Cr超过中国商品有机肥重金属限量标准、欧盟生态标志法的重金属限量标准、加拿大堆肥重金属限量标准(A级)和加拿大堆肥重金属限量标准(B级);As、Cd超过中国商品有机肥重金属限量标准、欧盟生态标志法的重金属限量标准和加拿大堆肥重金属限量标准(A级);Cu、Zn超过欧盟生态标志法的重金属限量标准和加拿大堆肥重金属限量标准(A级);Hg超过加拿大堆肥重金属限量标准(A级);Pb超过中国商品有机肥重金属限量标准;Ni均未超标.     

The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers

Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs.     

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.     

Influence of metal resistant-plant growth-promoting bacteria on the growth of Ricinus communis in soil contaminated with heavy metals

The metal resistant-plant growth-promoting bacterial (PGPB) strains PsM6 and PjM15 isolated from a serpentine soil were characterized as Pseudomonas sp. and Pseudomonas jessenii, respectively, on the basis of their morphological, physiological, biochemical characteristics and 16S rDNA sequences. Assessment of plant growth-promoting parameters revealed the intrinsic ability of the strains for the utilization of 1-aminocyclopropane-1-carboxylic acid as the sole N source, solubilization of insoluble phosphate and production of indole-3-acetic acid (IAA). Further, a pot experiment was conducted to elucidate the effects of inoculating metal resistant PGPB on the plant growth and the uptake of Ni, Cu and Zn by Ricinus communis. Inoculation of Pseudomonas sp. PsM6 or P. jessenii PjM15 increased the shoot and root biomass of R. communis grown in non-contaminated and contaminated soil. However, the maximum biomass was observed in the plants inoculated with strain PjM15. This effect can be attributed to the solubilization of phosphate and production of IAA. Inoculation of Pseudomonas sp. PsM6 and PjM15 did not greatly alter the organ metal concentrations except Zn which concentration was higher in root, stem and leaf of inoculated plants. The results of metal extraction with PGPB strains showed that PsM6 was more efficient at solubilizing Zn than PjM15, and that PjM15 was better at solubilising Ni and Cu than PsM6. Owing to its wide action spectrum, the metal resistant PGPB could serve as an effective metal sequestering and growth-promoting bioinoculant for plants in metal-stressed soil. The present study has provided a new insight into the phytoremediation of metal-contaminated soil.     

Fractionation of heavy metals and distribution of organic carbon in two contaminated soils amended with humic acids

The effects of humic acids (HAs) extracted from two different organic materials on the distribution of heavy metals and on organic-C mineralisation in two contaminated soils were studied in incubation experiments. Humic acids isolated from a mature compost (HAC) and a commercial Spaghnum peat (HAP) were added to an acid soil (pH 3.4; 966 mg kg(-1) Zn and 9,229 mg kg(-1) Pb as main contaminants) and to a calcareous soil (pH 7.7; 2,602 mg kg(-1) Zn and 1,572 mg kg(-1) Pb as main contaminants) at a rate of 1.1g organic-C added per 100g soil. The mineralisation of organic-C was determined by the CO(2) released during the experiment. After 2, 8 and 28 weeks of incubation the heavy metals of the soils were fractionated by a sequential extraction procedure. After 28 weeks of incubation, the mineralisation of the organic-C added was rather low in the soils studied (<8% of TOC in the acid soil; <10% of TOC in the calcareous soil). Both humic acids caused significant Zn and Pb immobilisation (increased proportion of the residual fraction, extractable only with aqua regia) in the acid soil, while Cu and Fe were slightly mobilised (increased concentrations extractable with 0.1M CaCl(2) and/or 0.5M NaOH). In the calcareous soil there were lesser effects, and at the end of the experiment only the fraction mainly related to carbonates (EDTA-extractable) was significantly increased for Zn and decreased for Fe in the humic acids treated samples. However, HA-metal interactions provoked the flocculation of these substances, as suggested by the association of the humic acids with the sand fraction of the soil. These results indicate that humic acid-rich materials can be useful amendments for soil remediation involving stabilisation, although a concomitant slight mobilisation of Zn, Pb and Cu can be provoked in acid soils.     

石灰干化污泥对土壤重金属稳定化处理的效果

以采自湖南省嘉禾县重金属复合污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP和BCR连续提取法对稳定化效果进行分析和评价。研究结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-98.92%、Cd-99.06%、Pb-96.84%;但是干化污泥的高pH值导致稳定后土壤中As的浸出增加。为了恢复植物生长功能,经过亚铁盐和磷酸调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时亚铁盐和磷酸有利于促进Pb和Zn的稳定效果;但是对Cd的稳定有负面影响;另外,亚铁盐的加入同时可以减少As的浸出浓度。经处理后土壤中重金属形态由不稳定态转为稳定态,使重金属的浸出浓度明显降低,减少了土壤重金属的浸出毒性。该研究结果表明,石灰干化污泥可以作为资源回收利用,应用于重金属污染土壤的修复中,并能改善稳定后土壤适宜植物生长的理化性质。     

Influence of initial pH on bioleaching of heavy metals from contaminated soil employing indigenous Acidithiobacillus thiooxidans

Bioleaching of heavy metals from contaminated soil was carried out employing indigenous sulfur oxidizing bacterium Acidithiobacillus thiooxidans. Experiments were carried out to assess the influence of initial pH of the system on bioleaching of chromium, zinc, copper, lead and cadmium from metal contaminated soil. pH at the end of four weeks of bioleaching at different initial pH of 3-7 was between 0.9 and 1.3, ORP between 567 and 617mV and sulfate production was in the range of 6090-8418mgl(-1). Chromium, zinc, copper, lead and cadmium solubilization ranged from "59% to 98%" at different initial pH. A. thiooxidans was not affected by the increasing pH of the bioleaching system towards neutral and it was able to utilize elemental sulfur. The results of the present study are encouraging to develop the bioleaching process for decontamination of heavy metal contaminated soil.     

液固比对含重金属水泥熟料制品中重金属释放的影响

通过模拟煅烧试验制取水泥熟料,参照JGJ 55-2000（《普通混凝土配比设计规程》）制取混凝土样品,参考SR003.1和NEN 7375浸出试验,分别研究液固比对粒状及块状混凝土样品中重金属（Cr、Ni和As）释放的影响。结果表明,在不同液固比条件下粒状混凝土中的重金属浸出浓度为Cr>Ni>As,Cr、As浸出浓度基本保持不变,分别为2 500 μg/L左右和5～6 μg/L,Ni在液固比（L∶S）<6时,浸出浓度随着液固比的增加而降低,在L∶S>6时,浸出浓度较稳定,为35.7～41.5 μg/L;浸出量均随着液固比的增加而增大。液固比（L∶S）<10时,块状混凝土中重金属累积释放量及扩散系数均随液固比的增加而增大,当L∶S>10时两者基本保持不变。     

污染土壤中重金属生物有效性的植物指示法研究

污染土壤中重金属生物活性的判断是污染土壤修复的关键所在。植物指示法是近年来发展起来的判断污染土壤中重金属生物可利用性的一种经济简便且可靠的方法。综述了近年来国内外科研工作者在重金属污染程度的植物指示方面所做的工作，重点阐述了用指示植物监测环境污染以及指示植物的选择问题。     

Influence of soil moisture on the sequestration of organic compounds in soil

A study was conducted as a part of continuing investigation of the effect of soil moisture on the sequestration of organic compounds aged in the soil. Here, experiments focused on the effects of moisture changes within the soil before, during, and after contaminant addition. The extractability of aged (68 d) phenanthrene was greater from soil that had been subjected to wetting and drying cycles prior to solute addition as compared to soil initially maintained at constant moisture. The recovery of phenanthrene added to moist soil was increased relative to extractability from soil that was air-dried at the time of the contaminant addition. Repeated wetting and drying of soil after the addition of atrazine or phenanthrene resulted in decreased extractability of the compounds as compared to samples maintained at constant moisture. A method for rapidly sequestering contaminants is proposed and may be useful in limiting the time required for laboratory studies involving “aged” contaminants. These data build upon the findings of earlier work from our laboratory and indicate that changes in the moisture conditions of soil can affect the availability of sequestered contaminants possibly through alterations in the structure of the natural solid.     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

Influence of heavy metals on the microbial degradation of diesel fuel

The degradation of diesel fuel by a microbial community from a soil polluted by heavy metals (h.m.) in the presence of Cu, Ni, Zn, Pb, Cd, Hg and Cr (as chromate) was investigated. Experiments were conducted with soil slurries and the extracted community in liquid cultivation. The concentrations applied were in the sub-mM and mM range. Whereas the slurries displayed no significant effect, degradation in liquid culture was increasingly inhibited by higher metal concentrations. The course of degradation in suspension was demonstrated by the oxygen consumption. The order of toxicity was found to be: Hg > Cr(VI) > Cu > Cd > Ni > Pb > Zn. The absence of any effect for slurries was due to the non-availability of the metals in the soil, and to precipitation or adsorption to the soil in the case of amendment. The paper also includes results on the availability of h.m. and changes to the community after exposure.     

Extractable soil heavy metals following the cessation of biosolids application to agricultural soil

Changes in soil heavy metal extractability following the cessation of biosolids applications were studied in a long-term field experiment. Two anaerobically digested biosolids from wastewater treatment plants in Madrid (Sur and Viveros) were applied to cropland from 1983 to 1990. Soil samples were collected in the 1st, 5th and 9th year after the last biosolids application. Soil pH did not vary significantly after biosolids applications. Organic matter and total heavy metals (Zn, Pb, Cd, Ni, Cr and Cu) concentrations initially increased but then declined over time, mostly after the first 5 years following biosolids application. Metal extracted with DPTA increased in Sur treatments during the 1st year and diminished thereafter. However, in Viveros treatments, heavy metals extracted increased during the 1st year, declined in 1995, and showed a slight increase in 1999. These changes in heavy metal extractability were widely observed in the percentage of extractable metal recovery (EMR). The differences observed in the pattern of the two sources of biosolids applied could be due to the different rates of decomposition of their organic matter.     

Mapping heavy metals in polluted soil by disjunctive kriging

The soil of some 50 km(2) around the town of Weinfelden in north-east Switzerland has been sampled and analysed to estimate and map the concentrations of heavy metals before an incinerator for the canton's waste is built. Given that the estimates are subject to error, the probabilities that true values exceed the maximum tolerable concentrations of the Swiss federal guide have also been estimated by disjunctive kriging. These may now be used by the local planners for making decisions. Of the metals examined, lead exceeded the guide value at several sampling points, and a moderate probability of excess of lead is fairly widespread. Copper exceeded the guide value in vineyards and orchards, but also in a few places elsewhere, and the estimated probabilities of excess were not negligible. The other two metals of concern, cadmium (with one exception) and zinc, had concentrations much less than the guide values. The patterns of distribution of the four metals were similar, the product-moment correlations among them are substantial, except in the vineyards and orchards, and it seems likely that they had common sources.